Catalyst, method of producing the catalyst, and polymerization process employing the catalyst

Abstract

A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is mixed with a precipitating agent to form an active olefin polymerization catalyst. The catalyst can be further treated with a halide ion exchanging source to form an active olefin polymerization catalyst. Prepolymer is deposited on the catalyst(s) in an amount effective to reduce polymer fines when the catalyst(s) are used in polymerization processes.

That which is claimed is: 
     
       1. A method of making a catalyst comprising mixing a first catalyst component solution and a second catalyst component, wherein the first catalyst component is formed by the chemical combination of: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group IIB metals, and   (2) a transition metal compound in which the transition metals are selected from Groups IVB and VB and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides;   wherein the second catalyst component is a precipitating agent selected from the group consisting of (a) organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard Reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and hydrocarbyl aluminum halides, (b) metal halides and oxyhalides of metals of Group IIIA, IVA, IVB, VA, and VB, (c) hydrogen halides, and organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R'" is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and depositing prepolymer on said catalyst in an amount in the range of about 1 to about 50 weight percent of the prepolymerized catalyst, said prepolymer being formed by polymerizing monomers selected from the group consisting of aliphatic mono-1-olefins and conjugated dienes.   
     
     
       2. A method according to claim 1 wherein said transition metal compound is of the formula Ti(OR) 4  wherein each R is individually selected from alkyl radicals containing 1 to 10 carbon atoms per radical. 
     
     
       3. A method according to claim 2 wherein said metal halide compound is magnesium dichloride. 
     
     
       4. A method according to claim 3 wherein said transition metal compound is titanium tetraethoxide. 
     
     
       5. A method according to claim 4 wherein the molar ratio of titanium to magnesium in the reactants used to make said first catalyst component are in the range of about 2:1 to about 1:2. 
     
     
       6. A method according to claim 5 wherein the solid product resulting from the reaction of said first and second catalyst components is further reacted with a halide ion exchanging source selected from the group consisting of titanium tetrahalides, vanadium oxychloride, and zirconium tetrachloride. 
     
     
       7. A method according to claim 6 wherein said halide ion exchanging source is titanium tetrachloride. 
     
     
       8. A method according to claim 7 wherein said prepolymer is deposited on the catalyst after treatment with the titanium tetrachloride. 
     
     
       9. A method according to claim 7 wherein said prepolymer is deposited on the catalyst prior to treatment with the titanium tetrachloride. 
     
     
       10. A method according to claim 9 wherein said titanium tetrachloride treatment is conducted at a temperature in the range of about 15° C. to about 50° C. 
     
     
       11. A method according to claim 10 wherein the prepolymer is deposited in such an amount that about 3 to 40 weight percent of the prepolymerized catalyst is prepolymer. 
     
     
       12. A method according to claim 11 wherein said prepolymer is polyethylene. 
     
     
       13. A method according to claim 12 wherein the second catalyst component is selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum dioiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, methyl-n-propylaluminum bromide, di-n-octylluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiiodide. 
     
     
       14. A method according to claim 12 wherein said second catalyst component is ethylaluminum sesquichloride. 
     
     
       15. A method according to claim 7 wherein said second catalyst component is ethylaluminum sesquichloride. 
     
     
       16. A method according to claim 1 wherein the solid product resulting from the reaction of said first and second catalyst components is further reacted with a halide ion exchanging source selected from the group consisting of titanium tetrahalides, vanadium, oxychloride, and zirconium tetrachloride. 
     
     
       17. A method according to claim 16 wherein: the metal halide compound is selected from the group consisting of beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium bromide, magnesium hydroxychloride, magnesium diodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride;   the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyloxides, titanium tetraimides, titanium tetraamides, titanium tetramercaptides, zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides, and vanadium tetramercaptides;   the second catalyst component is selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum dioiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, methyl-n-propylaluminum bromide, di-n-octylluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiiodide; and   the halide ion exchanging source is titanium tetrachloride.   
     
     
       18. A method according to claim 16 wherein: the metal halide compound is selected from the group consisting of magnesium dihalides;   the transition metal compound is selected from the group consisting of titanium tetraalkoxides;   the second catalyst component is selected from the group consisting of ethylaluminum sesquichloride, ethylaluminum dichloride, and diethylaluminum chloride; and   the halide ion exchanging source is titanium tetrachloride.   
     
     
       19. A method according to claim 16 wherein: the prepolymer comprises polymer polymerized from at least one monomer selected from the group consisting of aliphatic mono-1-olefins having from 2 to about 20 carbon atoms per molecule and conjugated dienes having from 4 to about 8 carbon atoms per molecule.   
     
     
       20. A catalyst comprising the product resulting from the method of any one of claims 1-19. 
     
     
       21. A catalyst according to claim 20 further comprising a cocatalyst selected from the group consisting of organometallic compounds represented by the general formulas   R"AlX.sub.2       R".sub.2 AlX       R'.sub.3 Al.sub.2 X.sub.3 and       R".sub.3 Al     in which R" is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms per radical and each R" can be the same or different, and X is a halogen atom.   
     
     
       22. A catalyst according to claim 20 wherein said cocatalyst comprises triethylaluminum.